3,7,11,19,23,27-Hexaaza-tricyclo-[27.3.1.1]tetra-triaconta-1(32),13,15,17(34),29(33),30-hexa-ene hexa-chloride tetra-hydrate.

The title compound, C(28)H(52)N(6) (6+)·6Cl(-)·4H(2)O, is a dinucleating 28-membered centrosymmetric hexa-azamacrocyclic complex. The macrocyclic ligand adopts a chair-like conformation, with the crystallographic inversion center located in the macrocyclic cavity. The six chloride ions and four water mol-ecules are situated symmetrically outside the macrocyclic cavity. The crystal structure is stabilized by N-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonds.

Related literature

For studies on hexa­azamacrocyclic complexes, see: Llobet et al. (1994 ▶). For related literature, see: Anda et al. (2000 ▶); Costas et al. (2004 ▶); Lu et al. (1995 ▶).

Experimental

Crystal data

C28H52N6 6+·6Cl−·4H2O

M = 757.52

Monoclinic,

a = 17.012 (7) Å

b = 7.469 (2) Å

c = 17.329 (7) Å

β = 113.841 (13)°

V = 2014.0 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.46 mm−1

T = 293 (2) K

0.19 × 0.18 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (Higashi, 1995 ▶) T min = 0.895, T max = 0.932

18546 measured reflections

4594 independent reflections

2416 reflections with I > 2σ(I)

R int = 0.102

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.130

S = 1.04

4594 reflections

235 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.26 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 1990 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063064/ci2525sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063064/ci2525Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C28H52N66+·6Cl–·4H2O	F000 = 808
Mr = 757.52	Dx = 1.249 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 4594 reflections
a = 17.012 (7) Å	θ = 3.0–27.5º
b = 7.469 (2) Å	µ = 0.46 mm−1
c = 17.329 (7) Å	T = 293 (2) K
β = 113.841 (13)º	Block, colourless
V = 2014.0 (13) Å3	0.19 × 0.18 × 0.15 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	4594 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.102
Detector resolution: 10.0 pixels mm-1	θmax = 27.5º
T = 293(2) K	θmin = 3.0º
ω scans	h = −22→22
Absorption correction: multi-scan(Higashi, 1995)	k = −9→8
Tmin = 0.895, Tmax = 0.932	l = −22→22
18546 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130	w = 1/[σ2(Fo2) + (0.0489P)2 + 0.1273P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
4594 reflections	Δρmax = 0.24 e Å−3
235 parameters	Δρmin = −0.26 e Å−3
8 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.82877 (18)	0.1791 (4)	0.39938 (18)	0.0355 (7)
C2	0.84179 (18)	0.0147 (4)	0.44031 (19)	0.0368 (7)
H2	0.8105	−0.0843	0.4115	0.044*
C3	0.90031 (19)	−0.0047 (4)	0.52305 (19)	0.0350 (7)
C4	0.94848 (19)	0.1433 (4)	0.5644 (2)	0.0400 (8)
H4	0.9890	0.1320	0.6196	0.048*
C5	0.9369 (2)	0.3061 (4)	0.5244 (2)	0.0450 (8)
H5	0.9693	0.4044	0.5528	0.054*
C6	0.8769 (2)	0.3245 (4)	0.4419 (2)	0.0420 (8)
H6	0.8692	0.4351	0.4151	0.050*
C7	0.76289 (18)	0.1935 (5)	0.30992 (19)	0.0431 (8)
H7A	0.7856	0.2686	0.2781	0.052*
H7B	0.7527	0.0754	0.2845	0.052*
C8	0.63910 (18)	0.1810 (4)	0.35545 (18)	0.0367 (7)
H8A	0.6756	0.1954	0.4149	0.044*
H8B	0.6329	0.0539	0.3428	0.044*
C9	0.55173 (19)	0.2631 (4)	0.33619 (19)	0.0395 (8)
H9A	0.5580	0.3911	0.3465	0.047*
H9B	0.5149	0.2447	0.2771	0.047*
C10	0.51067 (18)	0.1803 (4)	0.39031 (19)	0.0385 (7)
H10A	0.5066	0.0517	0.3820	0.046*
H10B	0.5460	0.2037	0.4493	0.046*
C11	0.37784 (18)	0.1881 (4)	0.41939 (19)	0.0411 (8)
H11A	0.4035	0.2392	0.4756	0.049*
H11B	0.3838	0.0590	0.4245	0.049*
C12	0.28364 (19)	0.2373 (4)	0.3786 (2)	0.0435 (8)
H12A	0.2782	0.3645	0.3663	0.052*
H12B	0.2566	0.1734	0.3256	0.052*
C13	0.23772 (18)	0.1922 (4)	0.4348 (2)	0.0412 (8)
H13A	0.2536	0.0728	0.4577	0.049*
H13B	0.2544	0.2762	0.4814	0.049*
C14	0.08870 (19)	0.1827 (4)	0.4337 (2)	0.0434 (8)
H14A	0.0289	0.1977	0.3957	0.052*
H14B	0.1033	0.2769	0.4757	0.052*
N1	0.67900 (17)	0.2703 (4)	0.30374 (17)	0.0345 (6)
H1A	0.683 (2)	0.3817 (17)	0.3174 (19)	0.049 (10)*
H1B	0.6425 (19)	0.256 (4)	0.2505 (19)	0.037 (8)*
N2	0.42311 (16)	0.2566 (4)	0.36763 (17)	0.0341 (6)
H2A	0.4253 (18)	0.375 (4)	0.3706 (18)	0.038 (9)*
H2B	0.391 (2)	0.238 (4)	0.309 (2)	0.052 (10)*
N3	0.14354 (16)	0.2017 (4)	0.38479 (18)	0.0385 (6)
H3A	0.129 (2)	0.303 (2)	0.3601 (18)	0.053 (11)*
H3B	0.130 (2)	0.120 (3)	0.3470 (14)	0.046 (10)*
O1W	0.2694 (2)	0.7467 (6)	0.4322 (2)	0.1099 (12)
H1O	0.226 (2)	0.690 (7)	0.400 (3)	0.165*
H2O	0.307 (2)	0.711 (8)	0.416 (4)	0.165*
O2W	0.09052 (17)	−0.0279 (3)	0.24667 (18)	0.0595 (7)
H3O	0.090 (3)	−0.1386 (18)	0.256 (3)	0.089*
H4O	0.0390 (11)	0.005 (5)	0.232 (3)	0.089*
Cl1	0.43151 (6)	0.67844 (11)	0.38468 (5)	0.0500 (2)
Cl2	0.68078 (6)	0.68054 (11)	0.32358 (5)	0.0545 (3)
Cl3	0.10025 (6)	0.55940 (11)	0.28508 (6)	0.0543 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0243 (15)	0.0496 (19)	0.0374 (16)	0.0022 (15)	0.0175 (13)	0.0018 (15)
C2	0.0258 (15)	0.0446 (18)	0.0432 (17)	−0.0034 (13)	0.0172 (14)	−0.0063 (15)
C3	0.0252 (15)	0.0397 (17)	0.0454 (18)	0.0035 (13)	0.0197 (14)	0.0033 (15)
C4	0.0295 (16)	0.054 (2)	0.0393 (17)	−0.0024 (15)	0.0172 (14)	0.0001 (16)
C5	0.0406 (19)	0.0457 (19)	0.0478 (19)	−0.0110 (15)	0.0169 (16)	−0.0032 (16)
C6	0.0391 (18)	0.0430 (18)	0.0475 (19)	−0.0013 (15)	0.0213 (15)	0.0061 (16)
C7	0.0331 (17)	0.064 (2)	0.0373 (17)	0.0027 (16)	0.0192 (14)	−0.0028 (16)
C8	0.0329 (16)	0.0444 (17)	0.0362 (16)	0.0022 (14)	0.0174 (14)	0.0044 (14)
C9	0.0350 (17)	0.0436 (17)	0.0449 (18)	0.0044 (14)	0.0210 (15)	0.0038 (15)
C10	0.0293 (16)	0.0456 (18)	0.0400 (17)	0.0042 (14)	0.0133 (14)	0.0056 (15)
C11	0.0302 (16)	0.0512 (19)	0.0434 (18)	−0.0002 (15)	0.0165 (14)	0.0063 (16)
C12	0.0327 (17)	0.053 (2)	0.0496 (19)	0.0028 (15)	0.0213 (15)	0.0107 (16)
C13	0.0279 (16)	0.054 (2)	0.0423 (17)	−0.0007 (15)	0.0151 (14)	0.0043 (16)
C14	0.0343 (17)	0.0475 (19)	0.057 (2)	0.0081 (15)	0.0279 (16)	0.0075 (16)
N1	0.0321 (14)	0.0430 (17)	0.0290 (14)	−0.0003 (13)	0.0130 (12)	−0.0010 (13)
N2	0.0267 (14)	0.0355 (15)	0.0413 (16)	−0.0016 (12)	0.0152 (12)	−0.0004 (13)
N3	0.0328 (14)	0.0379 (16)	0.0460 (16)	0.0016 (13)	0.0170 (13)	0.0068 (15)
O1W	0.077 (2)	0.147 (3)	0.101 (3)	−0.015 (2)	0.031 (2)	−0.065 (2)
O2W	0.0507 (16)	0.0587 (15)	0.0750 (17)	−0.0019 (14)	0.0317 (15)	−0.0071 (15)
Cl1	0.0533 (5)	0.0491 (5)	0.0392 (4)	−0.0022 (4)	0.0098 (4)	−0.0021 (4)
Cl2	0.0599 (6)	0.0452 (5)	0.0469 (5)	−0.0075 (4)	0.0096 (4)	−0.0035 (4)
Cl3	0.0492 (5)	0.0495 (5)	0.0622 (6)	−0.0017 (4)	0.0206 (4)	0.0085 (4)

C1—C6	1.380 (4)	C11—N2	1.489 (4)
C1—C2	1.391 (4)	C11—C12	1.512 (4)
C1—C7	1.505 (4)	C11—H11A	0.97
C2—C3	1.383 (4)	C11—H11B	0.97
C2—H2	0.93	C12—C13	1.512 (4)
C3—C4	1.390 (4)	C12—H12A	0.97
C3—C14i	1.500 (4)	C12—H12B	0.97
C4—C5	1.374 (4)	C13—N3	1.483 (4)
C4—H4	0.93	C13—H13A	0.97
C5—C6	1.387 (4)	C13—H13B	0.97
C5—H5	0.93	C14—N3	1.500 (4)
C6—H6	0.93	C14—C3i	1.500 (4)
C7—N1	1.501 (4)	C14—H14A	0.97
C7—H7A	0.97	C14—H14B	0.97
C7—H7B	0.97	N1—H1A	0.861 (10)
C8—N1	1.483 (4)	N1—H1B	0.89 (3)
C8—C9	1.515 (4)	N2—H2A	0.89 (3)
C8—H8A	0.97	N2—H2B	0.95 (3)
C8—H8B	0.97	N3—H3A	0.857 (10)
C9—C10	1.510 (4)	N3—H3B	0.857 (10)
C9—H9A	0.97	O1W—H1O	0.84 (4)
C9—H9B	0.97	O1W—H2O	0.84 (5)
C10—N2	1.492 (4)	O2W—H3O	0.841 (10)
C10—H10A	0.97	O2W—H4O	0.84 (3)
C10—H10B	0.97
C6—C1—C2	119.0 (3)	N2—C11—H11A	109.7
C6—C1—C7	121.9 (3)	C12—C11—H11A	109.7
C2—C1—C7	119.1 (3)	N2—C11—H11B	109.7
C3—C2—C1	121.4 (3)	C12—C11—H11B	109.7
C3—C2—H2	119.3	H11A—C11—H11B	108.2
C1—C2—H2	119.3	C13—C12—C11	111.7 (3)
C2—C3—C4	118.6 (3)	C13—C12—H12A	109.3
C2—C3—C14i	120.1 (3)	C11—C12—H12A	109.3
C4—C3—C14i	121.3 (3)	C13—C12—H12B	109.3
C5—C4—C3	120.7 (3)	C11—C12—H12B	109.3
C5—C4—H4	119.7	H12A—C12—H12B	107.9
C3—C4—H4	119.7	N3—C13—C12	109.3 (3)
C4—C5—C6	120.2 (3)	N3—C13—H13A	109.8
C4—C5—H5	119.9	C12—C13—H13A	109.8
C6—C5—H5	119.9	N3—C13—H13B	109.8
C1—C6—C5	120.2 (3)	C12—C13—H13B	109.8
C1—C6—H6	119.9	H13A—C13—H13B	108.3
C5—C6—H6	119.9	N3—C14—C3i	112.7 (2)
N1—C7—C1	113.0 (2)	N3—C14—H14A	109.1
N1—C7—H7A	109.0	C3i—C14—H14A	109.1
C1—C7—H7A	109.0	N3—C14—H14B	109.1
N1—C7—H7B	109.0	C3i—C14—H14B	109.1
C1—C7—H7B	109.0	H14A—C14—H14B	107.8
H7A—C7—H7B	107.8	C8—N1—C7	116.1 (2)
N1—C8—C9	109.4 (2)	C8—N1—H1A	106 (2)
N1—C8—H8A	109.8	C7—N1—H1A	112 (2)
C9—C8—H8A	109.8	C8—N1—H1B	106 (2)
N1—C8—H8B	109.8	C7—N1—H1B	106 (2)
C9—C8—H8B	109.8	H1A—N1—H1B	110 (3)
H8A—C8—H8B	108.2	C11—N2—C10	114.5 (2)
C10—C9—C8	110.9 (2)	C11—N2—H2A	109 (2)
C10—C9—H9A	109.5	C10—N2—H2A	110.6 (19)
C8—C9—H9A	109.5	C11—N2—H2B	112 (2)
C10—C9—H9B	109.5	C10—N2—H2B	108 (2)
C8—C9—H9B	109.5	H2A—N2—H2B	102 (3)
H9A—C9—H9B	108.1	C13—N3—C14	115.9 (3)
N2—C10—C9	110.1 (2)	C13—N3—H3A	111 (2)
N2—C10—H10A	109.6	C14—N3—H3A	104 (2)
C9—C10—H10A	109.6	C13—N3—H3B	108 (2)
N2—C10—H10B	109.6	C14—N3—H3B	109 (2)
C9—C10—H10B	109.6	H3A—N3—H3B	108 (3)
H10A—C10—H10B	108.2	H1O—O1W—H2O	102 (5)
N2—C11—C12	110.0 (2)	H3O—O2W—H4O	105 (4)
C6—C1—C2—C3	1.6 (5)	C2—C1—C7—N1	99.6 (3)
C7—C1—C2—C3	−178.7 (3)	N1—C8—C9—C10	−177.8 (3)
C1—C2—C3—C4	−2.0 (5)	C8—C9—C10—N2	−177.3 (2)
C1—C2—C3—C14i	178.4 (3)	N2—C11—C12—C13	−172.3 (3)
C2—C3—C4—C5	1.4 (5)	C11—C12—C13—N3	−166.5 (3)
C14i—C3—C4—C5	−179.1 (3)	C9—C8—N1—C7	−174.9 (2)
C3—C4—C5—C6	−0.3 (5)	C1—C7—N1—C8	−53.3 (4)
C2—C1—C6—C5	−0.5 (5)	C12—C11—N2—C10	−166.3 (3)
C7—C1—C6—C5	179.8 (3)	C9—C10—N2—C11	−178.1 (3)
C4—C5—C6—C1	−0.2 (5)	C12—C13—N3—C14	−172.8 (3)
C6—C1—C7—N1	−80.7 (4)	C3i—C14—N3—C13	−62.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2	0.86 (2)	2.24 (1)	3.082 (3)	168 (3)
N1—H1B···Cl1ii	0.89 (3)	2.24 (3)	3.115 (3)	169 (3)
O1W—H1O···Cl3	0.84 (4)	2.46 (5)	3.287 (4)	169 (4)
N2—H2A···Cl1	0.89 (3)	2.28 (3)	3.162 (3)	177 (3)
N2—H2B···Cl2ii	0.95 (3)	2.17 (3)	3.113 (3)	177 (3)
O1W—H2O···Cl1	0.84 (5)	2.40 (5)	3.222 (4)	166 (5)
N3—H3A···Cl3	0.85 (2)	2.25 (2)	3.104 (3)	173 (3)
N3—H3B···O2W	0.86 (2)	1.94 (2)	2.782 (4)	169 (2)
O2W—H3O···Cl3iii	0.84 (2)	2.30 (2)	3.144 (3)	176 (6)
O2W—H4O···Cl3iv	0.84 (3)	2.30 (3)	3.133 (4)	168 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2	0.86 (2)	2.24 (1)	3.082 (3)	168 (3)
N1—H1B⋯Cl1i	0.89 (3)	2.24 (3)	3.115 (3)	169 (3)
O1W—H1O⋯Cl3	0.84 (4)	2.46 (5)	3.287 (4)	169 (4)
N2—H2A⋯Cl1	0.89 (3)	2.28 (3)	3.162 (3)	177 (3)
N2—H2B⋯Cl2i	0.95 (3)	2.17 (3)	3.113 (3)	177 (3)
O1W—H2O⋯Cl1	0.84 (5)	2.40 (5)	3.222 (4)	166 (5)
N3—H3A⋯Cl3	0.85 (2)	2.25 (2)	3.104 (3)	173 (3)
N3—H3B⋯O2W	0.86 (2)	1.94 (2)	2.782 (4)	169 (2)
O2W—H3O⋯Cl3ii	0.84 (2)	2.30 (2)	3.144 (3)	176 (6)
O2W—H4O⋯Cl3iii	0.84 (3)	2.30 (3)	3.133 (4)	168 (4)

Symmetry codes: (i) ; (ii) ; (iii) .